Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
  • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
  • G02B1/041—Lenses
  • G02B1/043—Contact lenses
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate

Definitions

• This invention relates to a contact lens, and more specifically to a novel hydrous contact lens having excellent oxygen permeability.
• Contact lenses generally used at present are broadly classified into a hard contact lens and a soft contact lens.
• a soft contact lens a lens produced from a hydrous material containing polyhydroxyethyl methacrylate as a main component is widely used. Since, however, such a soft contact lens has insufficient oxygen permeability and insufficiently supplies the cornea with oxygen, a considerable burden is eventually imposed on the cornea due to oxygen deficiency when the soft contact lens is fitted on for a long period of time.
• JP-A-54-29660 a hydrous soft contact lens which is produced from a material having oxygen permeability in itself.
• the contact lens disclosed in the JP-A-54-29660 is formed essentially of a copolymer of 2-hydroxyethyl methacrylate (to be referred to as HEMA hereinafter) and perfluoroalkylethyl methacrylate (to be referred to as RfMA hereinafter), and this contact lens has attained an oxygen permeability of 500 to 2,708 centibarrels.
• HEMA 2-hydroxyethyl methacrylate
• RfMA perfluoroalkylethyl methacrylate
• a contact lens having an oxygen permeation coefficient of not less than 30 ⁇ 10 -11 [cm 3 (STP) cm/(cm 2 ⁇ sec ⁇ mmHg)] greatly reduces a burden which a contact lens would put on the cornea when fitted on.
• the contact lens disclosed in the above JP-A-54-29660 has an oxygen permeation coefficient of 5 ⁇ 10 -11 to 27 ⁇ 10 -11 [cm 3 (STP) cm/cm 2 ⁇ sec ⁇ mmHg)] after the conversion of the data disclosed therein, and it hence cannot be said that a sufficient oxygen permeation coefficient for reducing the burden on the cornea has been attained.
• the RfMA used as an essential component for the copolymer forming the above contact lens essentially has high hydrophobic nature, and therefore, in order to improve the fitting sense of the lens, it might be attempted to increase the water content of the lens by decreasing the RfMA content and increasing the HEMA content.
• This invention has been made in order to overcome the above problems, and provides a novel hydrous contact lens. It is an object of this invention to provide a contact lens having hydrous nature and sufficient oxygen permeability to reduce a burden which the contact lens might impose on the cornea when fitted on.
• fluorine-containing monomer of the above general formula (I) as an essential component for the copolymer constituting the contact lens of this invention are as follows.
• Examples of the group of ##STR5## in the above general formula (Ic) can include the following ca, cb and cc:
• the fluorine-containing hydrocarbon of C n F p H q helps to increase the oxygen permeability of a contact lens.
• the subindex "n” is limited to an integer of 4 to 10. That is because when “n” is an integer of 3 or less and “p" is an integer of 7 or less, the oxygen permeability is insufficient. And, when “n” is an integer of 11 or more, the resultant lens undesirably has fragility. Further, the more the number of fluorine atoms is, the higher the oxygen permeability is. Therefore, the subindex "p" is preferably an integer of 8 or more.
• the oxyethylene, oxypropylene or oxyethylene-oxypropylene group of the formula ##STR9## or ##STR10## helps to impart the polymer with hydrophilic nature, and also functions to improve the compatibility with a hydrophilic monomer which is the other essential component for the contact lens of this invention.
• the number of the above oxyethylene or oxypropylene group, i.e. l, is preferably an integer of 1 to 9.
• the reason therefor is as follows: When l is 0, the resultant fluorine-containing monomer shows poor compatibility with the hydrophilic monomer, and it is therefore difficult to obtain a transparent polymer by ordinary bulk polymerization. When l is an integer of 10 or more, it is difficult to obtain a pure monomer since l is distributed when the monomer is synthesized, and it is therefore difficult to obtain a copolymer having stable physical properties.
• the subindex "l” is preferably an integer of 1 to 5.
• the number of the oxyethylene-oxypropylene group, i.e. l 1 is preferably an integer of 2 to 9.
• the reason therefor is as follows: When l 1 is 1, no oxyethylene-oxypropylene group is constituted. When, l 1 is 10 or more, it is also similarly difficult to obtain a copolymer having stable physical properties.
• the subindex "l 1 " is preferably an integer of 2 to 5.
• the group of --CH 2 ) m in the above general formula is required to be present in order to obviate problems of hydrolysis, etc., which the fluorine-containing monomer might undergo, and to keep the monomer as a stable compound.
• the subindex "m" is preferably an integer of 1 to 5, more preferably an integer of 1 to 2.
• fluorine-containing monomer groups of the general formulae (Ia), (Ib) and (Ic) are preferably as follows. ##STR11##
• the fluorine-containing monomer of the general formula (I) for use in the copolymer constituting the hydrous contact lens of this invention represents at least one monomer selected from the above monomer groups (a), (b) and (c).
• said fluorine-containing monomer represents (i) one monomer selected from the monomer groups (a), (b) and (c), (ii) a combination of at least two monomers selected from one of the monomer groups (a), (b) and (c) [e.g. a combination of two monomers selected from the monomer group (a) alone], or (iii) a combination of at least two monomers selected from at least two different groups of the monomer groups (a), (b) and (c) [e.g. a combination of one monomer selected from the monomer group (a) and one monomer selected from the monomer group (b)].
• the amount of the fluorine-containing monomer is preferably 10 to 95 parts by weight (to be referred to as "part" hereinafter). When this amount is less than 10 parts, the desired oxygen permeability cannot be obtained. When it exceeds 95 parts, the hydrous nature cannot be obtained. Said amount is more preferably 20 to 80 parts.
• the hydrophilic monomer as other essential component for the copolymer constituting the hydrous contact lens of this invention contributes to obtaining a contact lens imparted with hydrous nature and to improvement in the contact lens fitting sense.
• This hydrophilic monomer can be selected from, for example, hydroxyalkyl (meth)acrylates [the term "(meth)acrylate” means both acrylate and methacrylate, and will be used in this sense hereinafter] typified by 2-hydroxyethylacrylate (to be referred to as "HEA” hereinafter) and HEMA; N-vinyllactams typified by N-vinylpyrrolidone (to be referred to as "NVP"), N-vinylpiperidone and N-vinylcaprolactam; amide-containing monomers such as N,N-dialkyl(meth)acrylamides typified by N,N-dimethyl(meth)acrylamide and N,N-diethyl(meth)acrylamide and monoalky
• At least one monomer of these is used.
• these hydrophilic monomers particularly preferred are HEMA, HEA, NVP and N,N-dimethylacrylamide (to be referred to as "DMAA").
• the amount of the hydrophilic monomer for use in this invention is preferably 5 to 90 parts. When this amount is less than 5 parts, the hydrous nature is undesirably insufficient. When it exceeds 90 parts, there is an undesirable possibility of the resultant copolymer being opaque. Said amount is more preferably 20 to 80 parts.
• a bulk polymerization method When a bulk polymerization method is employed to obtain a transparent copolymer having suitable hydrous nature and oxygen permeability, the following amounts for some of the above hydrophilic monomers are preferred; HEA: 20-50 parts, HEMA: 20-40 parts, NVP: 20-40 parts and DMAA: 20-80 parts.
• a monomer composition containing 10 to 50 parts of a compatibilizing diluent such as t-butyl alcohol, butyl cellosolve, or the like is cast-molded, or polymerized in a solution form, instead of carrying out the bulk polymerization, a transparent copolymer can be obtained without limiting the amount of the hydrophilic monomer to the above range.
• copolymer forming the contact lens of this invention Concerning the copolymer forming the contact lens of this invention, optional components may be incorporated as required in order to further improve the copolymer in physical properties.
• a crosslinking monomer may be incorporated.
• the crosslinking monomer can be selected, for example, from ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, allyl (meth)acrylate, glycerol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, triallylisocyanurate, 1,4-butanediol di(meth)acrylate, divinylbenzene, etc.
• These crosslinking monomers may be used alone or in combination.
• the amount of the crosslinking monomer is preferably 0.01 to 5 parts per 100 parts of the mixture of the fluorine-containing monomer of the above general formula (I) with the hydrophilic monomer. When this amount is less than 0.01 part, the form maintainability of the resultant contact lens is poor. When it exceeds 5 parts, the contact lens undesirability shows degraded flexibility and fragility.
• the copolymer may be formed by incorporating alkyl (meth)acrylate such as methyl (meth)acrylate, butyl (meth)acrylate, etc., fluorine-containing alkyl (meth)acrylate, silicone-containing (meth)acrylate, alicyclic or aromatic (meth)acrylate, and the like.
• alkyl (meth)acrylate such as methyl (meth)acrylate, butyl (meth)acrylate, etc.
• fluorine-containing alkyl (meth)acrylate such as methyl (meth)acrylate, butyl (meth)acrylate, etc.
• fluorine-containing alkyl (meth)acrylate such as methyl (meth)acrylate, butyl (meth)acrylate, etc.
• fluorine-containing alkyl (meth)acrylate such as methyl (meth)acrylate, butyl (meth)acrylate, etc.
• silicone-containing (meth)acrylate such as silicone-containing (
• the polymerization method for producing the copolymer forming the contact lens of this invention will be described below.
• the polymerization may be carried out according to any of known polymerization methods such as a bulk polymerization method, solution polymerization method, etc. Particularly preferred is a bulk polymerization method.
• a polymerization initiator at least one radical generator is generally used for the polymerization.
• the polymerization initiator can be selected, for example, from azobis compounds such as azobisisobutyronitrile, azobisdimethylvaleronitrile, etc., and peroxides such as benzoyl peroxide.
• the amount of the polymerization initiator is preferably 0.01 to 3% by weight per 100 parts of the total monomer mixture.
• the polymerization is carried out by casting the monomer mixture into a casting container made of a metal, glass, plastic, etc., closing the casting container, and elevating the temperature of the monomer mixture stepwise or continuously in a water bath or a hot air dryer.
• the polymerization temperature range is generally 20° to 150° C.
• the polymerization time is about 3 to about 72 hours.
• the resultant polymerizate or polymer is cooled to room temperature, taken out of the container, and subjected to ordinary machining and polishing to finish it into a contact lens form. Then, the finished lens is hydrated with water, 0.9% physiological saline or an isotonic buffer solution to obtain a hydrous contact lens.
• the polymerization to obtain the copolymer forming the contact lens of this invention is not limited to the above heat-applied polymerization, and may be carried out by ultraviolet light-applied polymerization or by cast polymerization by which the monomer mixture is formed directly into a contact lens form.
• a sample having a thickness of 0.2 mm was measured in 0.9% physiological saline having a temperature of 35° C. with a film oxygen transmissometer of Seika type supplied by Rikaseiki Kogyo K.K.
• the purpose of this measurement is to evaluate the transparency of a polymer.
• a sample having a thickness of 0.2 mm was measured in a 0.9% physiological saline with a recording spectrophotometer Model 330 Manufactured by Hitachi Ltd.
• a solution consisting of 55 parts of OPMA1, 45 parts of HEMA, 50 parts of tert-butyl alcohol (“t-BuL” hereinafter) and a benzoin isobutyl ether photosensitive initiator (“BBE” hereinafter) was filtered under reduced pressure to remove gases and suspended particles, and immediately thereafter, poured into a polymerization cell formed of two glass sheets of which the surfaces were fixed with a fluorinated ethylenepropylene polymer film. Radiation from two BL fluorescent lamps was focused to the cell at room temperature for 17 hours, and the resultant alcohol solvation polymer was immersed in a physiological saline at a room temperature and allowed to stand as it was to replace the alcohol with water, whereby a sample for measurement of contact lens properties was obtained. The sample was measured for physical properties in the same way as in Example 1. Table 1 shows the results.
• HEMA and RfMA HEMA and RfMA (RfMA means perfluorohexylethyl methacrylate in this Comparative Example, and will be used in this sense hereinafter) of which the amounts are shown in Table 1 were subjected to the same production procedure as that in Example 1, whereby a contact lens was obtained. The contact lens was measured for physical properties. Table 1 shows the results.
• HEMA and RfMA of which the amounts are shown in Table 1 were mixed with 50 parts of t-BuL and BBE to form a solution, and the solution was subjected to the same production procedure as that in Example 41 to prepare samples. The samples were measured for physical properties, and Table 1 shows the results.
• HEMA was subjected to the same production procedure as that in Example 1 to obtain a contact lens (formed of an HEMA homopolymer).
• Table 1 shows the physical properties thereof.
• RfMA Perfluoroalkylethyl methacrylate (Perfluorohexylethyl methacrylate was used.)
• NVP N-Vinylpyrrolidone
• TSM Tris(trimethylsiloxy)silylpropyl methacrylate
• the contact lens formed of a homopolymer of HEMA, obtained in Comparative Example 4 exhibited a considerably lower oxygen permeation coefficient than the contact lenses obtained in the other Examples. Further, with regard to contact lenses formed of a RfMA/HEMA copolymer, the contact lens produced by an ordinary bulk polymerization method in Comparative Example 1 was opacified and became no transparent one, and the contact lenses produced by incorporating t-BuL, obtained in Comparative Examples 2 and 3, failed to satisfy any of the requirements of the water content and oxygen permeation coefficient.
• the contact lens obtained in Example 41 was transparent due to the incorporation of t-BuL although it had a large content of HEMA, and it had a sufficient water content and oxygen permeation coefficient.
• the contact lens of this invention is a transparent copolymer which can be obtained even by bulk polymerization, and it has hydrous nature and excellent oxygen permeability.

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• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Eyeglasses (AREA)

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• 1990
  • 1990-07-31 US US07/667,395 patent/US5302678A/en not_active Expired - Fee Related
  • 1990-07-31 AU AU60546/90A patent/AU640941B2/en not_active Ceased
  • 1990-07-31 WO PCT/JP1990/000973 patent/WO1991002279A1/ja active IP Right Grant
  • 1990-07-31 DE DE69019942T patent/DE69019942T2/de not_active Expired - Fee Related
  • 1990-07-31 EP EP90910886A patent/EP0436727B1/de not_active Expired - Lifetime
  • 1990-07-31 ES ES90910886T patent/ES2072440T3/es not_active Expired - Lifetime

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